A.-L. Lücke et al.: Palladium complexes of anionic N-heterocyclic carbenesꢂꢁꢀꢀꢀꢂ7
3
.3 General procedure for the synthesis of
the 1-(2,4-dinitrophenyl)arenes (23a–c)
7.69–7.72 (m, 1H, 4′-H), 7.72–7.73 (m, 1H, 7′-H), 7.79–7.81 (d,
H, J ꢀ=ꢀ 6.7 Hz, 6-H), 7.88–7.89 (d, 1H, J ꢀ=ꢀ 6.7 Hz, 9′-H), 8.58–
.59 (d, 1H, J ꢀ=ꢀ 6.7 Hz, 5-H), 8.74–8.75 (d, 1H, J ꢀ=ꢀ 6.7 Hz,
1
8
A sample of 0.075 g (0.2 mmol) of 1-chloro-2,4-dinitroben- 6′-H), 8.80–8.81 (d, 1H, J ꢀ=ꢀ 6.7 Hz, 5′-H), 8.97–8.98 (s, 1H,
zene (22) was dissolved in 8 mL of anhydrous dioxane 3-H) ppm. – C NMR (CDCl + TMS): δ ꢀ=ꢀ 120.0 (C3), 122.7
1
3
3
under an atmosphere of nitrogen. Then, 0.010 g (5 mol%) (C6′), 123.4 (C5′), 125.1 (C2′), 126.8 (C5), 127.17 (C10′), 127.27
of the cis/trans-bromo-(N-phenylsydnone)palladium (C4′), 127.29 (C3′), 127.31 (C8′), 127.82 (C7′), 129.0 (C9′), 129.7
complex 9 (catalyst III) was added, the mixture was sub- (C1a′), 130.5 (C5a′), 130.6 (C9a′), 130.7 (C5b′), 132.3 (C1′),
jected to ultrasound irradiation for 5 min and then stirred 134.6 (C6), 141.7 (C1), 147.5 (C4), 149.8 (C2) ppm. – IR (ATR):
−1
at room temperature over a period of 25 min. Then, the 3112, 2852, 1941, 1537, 1518, 1342 cm . – MS (EI, 70 eV): m/z
+
corresponding boronic acid, 1.13 g (10.6 mmol) of sodium (%) ꢀ=ꢀ 344.1 (100) [M] . – HRMS (EI, 70 eV): m/z ꢀ=ꢀ 344.0797
+
carbonate, and 2 mL of water were added, and the result- (calcd. 344.0797 for [C H N O ] ).
2
0
12
2
4
ing mixture was heated at a temperature of 70°C for
0 min. After cooling to room temperature, the mixture
3
was dried over magnesium sulfate and chromatographed 3.3.4 (4-Isopropylphenyl)methanol (25)
on silica gel (petroleum ether/dichloromethane 1:3).
A sample of 0.075 g (0.4 mmol) (4-bromophenyl)methanol
and 0.110 g (0.8 mmol) of isopropylboronic acid was used
in the general procedure of 2,5-diaryl-3,4-dinitrothiophene
3
.3.1 2,4-Dinitro-1,1′-biphenyl (23a)
(
12–17). The product was obtained as a brownish solid in
A sample of 0.146 g (1.2 mmol) of phenylboronic acid was 98% yield (0.059 g); m.p. 29.6°C. Spectroscopic data are
used. The product was obtained as yellowish solid in 99% in agreement with those reported in the literature [45–50].
yield (0.089 g); m.p. 109.9°C. Spectroscopic data are in
agreement with those reported in the literature [52].
References
3
.3.2 1-(2,4-Dinitrophenyl)naphthalene (23b)
[
1] D. L. Browne, J. P. Harrity, Tetrahedron 2010, 66, 553.
2] T. L. Gilchrist in Science of Synthesis, Vol. 13, (Eds.: R. C. Storr,
T. L. Gilchrist), Thieme Verlag, Stuttgart, 2004, p. 109.
3] R. Chandrasekhar, M. J. Nanjan, Mini-Rev. Med. Chem. 2012,
12, 1359.
[
A sample of 0.208 g (1.0 mmol) of 1-naphthylboronic acid
[
was used. The product was obtained as yellowish solid in
1
95% yield (0.103 g); m.p. 115.8°C. – H NMR (CDCl + TMS):
3
[
[
[
4] J. C. Earl, A. W. Mackney, J. Chem. Soc. 1935, 899.
5] R. A. Eade, J. C. Earl, J. Chem. Soc. 1946, 591.
6] W. Baker, W. D. Ollis, Nature 1946, 158, 703.
δ ꢀ=ꢀ 7.34–7.37 (m, 2H, 4′-H/8′-H), 7.43–7.46 (t, 1 H, J ꢀ=ꢀ 6.7 Hz,
′-H), 7.52–7.56 (m, 2 H, 2′-H/7′-H), 7.72–7.73 (d, 1 H, J ꢀ=ꢀ 6.7
Hz, 6-H), 7.93–7.97 (m, 2 H, 5′-H/6′-H), 8.53–8.55 (m, 1 H,
3
[7] W. Baker, W. D. Ollis, V. D. Poole, J. Chem. Soc. 1949, 307.
[8] W. Baker, W. D. Ollis, V. D. Poole, J. Chem. Soc. 1950, 1542.
1
3
3
-H), 8.91–8.92 (d, 1 H, J ꢀ=ꢀ 6.7 Hz, 5-H) ppm. – C NMR
[
9] A. R. Katritzky, Chem. Ind. 1955, 521.
(
CDCl + TMS): δ ꢀ=ꢀ 119.9 (C3), 124.2 (C4′), 125.2 (C7′), 126.1
3
[
[
10] S. Wiechmann, T. Freese, M. H. H. Drafz, E. G. Hübner, J. C.
(
C8′), 126.6 (C2′), 126.7 (C5), 127.3 (C3′), 128.8 (C5′), 129.8
Namyslo, M. Nieger, A. Schmidt, Chem. Commun. 2014, 50,
(
C6′), 130.7 (C1a′), 133.2 (C1′), 133.5 (C5a′), 134.6 (C6), 141.7
1
1822.
(C1), 147.4 (C2), 149.8 (C4) ppm. – IR (ATR): 3105, 2854,
11] T. L. Gilchrist, P. M. O’Neill in Comprehensive Heterocyclic
Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven),
Elsevier, Pergamon, Oxford, 1996, p. 165.
−1
1
597, 1524, 1338, 1020, 969, 833 cm . – MS (EI, 70 eV): m/z
%) ꢀ=ꢀ 294.1 (100) [M] . – HRMS (EI, 70 eV): m/z ꢀ=ꢀ 294.0641
+
(
(
+
[12] C. A. Ramsden, Tetrahedron 2013, 69, 4146.
calcd. 294.0641 for [C H N O ] ).
16
10
2
4
[
[
[
13] C. A. Ramsden, W. P. Oziminski, Tetrahedron 2014, 70, 7158.
14] W. P. Oziminski, C. A. Ramsden, Tetrahedron 2015, 71, 7191.
15] W. D. Ollis, S. P. Stanforth, C. A. Ramsden, Tetrahedron 1985,
41, 2239.
3
.3.3 9-(2,4-Dinitrophenyl)phenanthrene (23c)
[
[
[
[
16] C. A. Ramsden, J. Chem. Soc., Chem. Commun. 1977, 109.
17] C. A. Ramsden, Adv. Heterocycl. Chem. 1980, 26, 1.
18] W. D. Ollis, C. A. Ramsden, Adv. Heterocycl. Chem. 1976, 19, 1.
19] C. G. Newton, C. A. Ramsden, Tetrahedron 1982, 38, 2965.
A sample of 0.208 g (1.0 mmol) of 9-phenanthrylboronic
acid was used. The product was obtained as yellowish
1
solid in 80% yield (0.102 g); m.p. 193.5°C. – H NMR (CDCl +
3
[20] H. Kato, M. Ohta, Bull. Chem. Soc. Jpn. 1959, 32, 282.
TMS): δ ꢀ=ꢀ 7.38–7.37 (d, 1H, 2′-H), 7.52–7.54 (t, 1H, J ꢀ=ꢀ 6.7 Hz,
[
21] S. N. Lebedev, I. A. Cherepanov, V. N. Kalinin, Russ. Chem.
Bull., Int. Ed. 2002, 51, 899.
3
′-H), 7.62 (s, 1H, 10′-H), 7.65–7.67 (t, 1H, J ꢀ=ꢀ 6.7 Hz, 8′-H),
Unauthenticated
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